US3291635A

US3291635A - Reaction products of copper and mercury salts and process for rendering cotton fabric rot resistant therewith

Info

Publication number: US3291635A
Application number: US356991A
Authority: US
Inventors: Charles J Conner
Original assignee: Individual
Current assignee: Individual
Priority date: 1964-04-02
Filing date: 1964-04-02
Publication date: 1966-12-13
Anticipated expiration: 1983-12-13

Description

United States Patent 3,291,635 REACTION PRODUCTS OF COPPER AND MER- CURY SALTS AND PROCESS FOR RENDERING COTTON FABRIC ROT RESISTANT THEREWITH Charles J. Conner, New Orleans, La., assignor to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Apr. 2, 1964, Ser. No. 356,991 16 Claims. (Cl. 117-1385) A nonexclusive, irrevocable royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

This application is a continuation-in-part of Serial No. 253,232, filed January 22, 1963, now US. Patent 3,183,- 118.

This invention relates to the formation, and subsequent deposition on cotton fabrics of complex water soluble derivatives, which are prepared by solubilizing copper and mercury salts, that are normally water insoluble, with zirconyl ammonium carbonate. Whereas Serial No. 253,232 relates to the water solubilizing of certain normally water insoluble copper and mercury salts via chemical reaction with zirconyl acetate to produce specific agents for textile treatment, the present continuationin-part application relates to derivatives produced by the chemical reaction of zirconyl ammonium carbonate (ammonium zirconyl carbonate) with certain normally water insoluble chemical compounds, of copper and mercury to the end that water soluble agents suitable for textile treatment are produced,

By process of this invention a copper borate and other water insoluble salts are made water soluble by treatment with zirconyl ammonium carbonate solutions. This treatment produces in the case of copper, a deep blue water soluble complex substance which can be later decomposed to form a derivative which is insoluble in water. Generally, the copper and mercury salts are easily and adequately soluble for use in treating textiles only in organic solvents, or they require solvent-emulsion systems for utilization.

Utility of water insoluble fungistatic and fungicidal agents is enhanced by the process of this invention in that the derivatives formed are water soluble, thereby making their commercial application more economical. Zirconyl ammonium carbonate has been used in textile treatments to produce water repellency in wax emulsions (Industrial and Engineering Chemistry, vol. 42, page 640, April 1950). Certain copper compounds have long been used as fungicidal textile treatments but their application has been limited by the necessity of application from organic solvents or emulsion systems (Fungusproofing of Textiles and Cordage for Use in Tropical Service, Office of Scientific Research and Development Report No. 4513, January 1945). Obviously, the use of water soluble chemicals reduces the cost of treatments.

The preferred concentration of zirconium oxide in the zirconyl ammonium carbonate solutions is about from 0.25% to 10.00%, calculated as ZrO These concentrations are ideal for the dissolution and com-plexing of the copper and mercury compounds in the zirconyl ammonium carbonate solutions. These deep blue copper complex solutions can be further solubilized in water, and have been prepared at concentrations about from 0.1% to 35% total solids, the blue coloration being visible at 'ice all concentrations. The mercury complex solutions are colorless, and have been prepared at concentrations about from 0.1% to 38.4% total solids.

Fungicidal activity has 'been established for both zirconium and the metal salts by Sin, Microbial Decomposition of Cellulose, Reinhold Publishing Corp, New York 1951, and the particular derivatives produced by process of this invention likewise have this quality. Algaecidal activity of zirconium has been noted by Conner, Cooper, Reeves, and Trask and reported in Some Microbial Resistant Compounds of Zirconium and Their Effect on Cotton (in manuscript). These water soluble compositions undergo a chemical change when heated, as indicated below, and this change is made manifest by the fact that the water soluble substance becomes insoluble when heated above a particular critical temperature, as based on the known mechanisms for zirconyl ammonium carbonate alone:

Note: The rate of decomposition is much faster when higher temperatures are employed (Ref.: Titanium Alloy Mfg. Division, Data File D-52, 5/28/59).

When a copper or mercury complex exists in the aqueous phase with zirconyl ammonium carbonate, decomposition by heating effectively results in precipitation of ZrO with the mercury or copper derivative as an insoluble residue. CO and NH are lost during the decomposition.

Other water soluble compositions capable of being prepared by the action of zirconyl ammonium carbonate solution upon the water insoluble salts of the heavy metals include compositions prepared from the following mercury salts:

Phenyl Mercury Acetate Phenyl Mercury Salicylate Phenyl Mercury Lactate Phenyl Mercury Propionate Phenyl Mercury Borate Phenyl Mercury Benzoate All the water soluble compositions prepared from the above listed salts, as well as those prepared from their homologs, can be applied to cotton to produce materials with fungistatic or fungicidal properties.

A suitable copper borate for solubilization is one containing a CuO to B 0 molar ratio about from 2:3 to 1:2. The copper borate may be hydrated or anhydrous. The appropriate zirconyl ammonium carbonate solutions are available commercially, zirconyl ammonium carbonate solution suitable for the purpose of this invention is one having the following specifications:

ZrO percent by weight 10.0 Molecular wt. of solute 378.39 Density of solution at 24 C. 1.238 pH at 24 C. 9.6

The reactants have the following formulae:

Zirconyl ammonium carbonate Copper borate Note: x and y represent molar ratios.

Phenyl mercury acetate (representative of phenyl mercury salts) The solubility of phenyl mercury salts in zirconyl ammonium carbonate solution (10% ZIO2) is complete up to 4.0% mercury and 95% soluble up to 4.24% mercury. The phenyl mercury acetate and propionate are completely soluble up to 4.1% mercury. The copper borate (1 CuO:2B O is soluble to the extent of 4% in the zirconyl ammonium carbonate (10% ZrO When an aqueous solution of the copper borate complex is evaporated to dryness, a blue insoluble granular compound is formed. This compound shows no evidence of solubility in water when washed and extracted with distilled water.

One explanation of the mechanisms involved in the preparation of these substances is here exemplified:

Copper borate-Zirconyl ammonium carbonate derivative (water soluble) theoretical molecular weight 833.88

In the case of phenyl mercury salts, i.e., acetate, the mechanism can be explained as follows:

In the case of decomposition of these complexes with heat the mechanism can be explained as follows:

The insoluble derivative from heat decomposition is blue-green and shows strong afiinity for cellulose, resisting four hours of water leaching without evidence of loss of material through solubility. The possibility of crosslinkage of zirconium compounds with cellulose is known, and the following suggested structure could explain the heat-decomposed copper borate-zirconyl ammonium carbonate residual:

insol. compd. CUBzOA- (ZI'Oz) z ZHaO HOBOZ"r-OH Insoluble (deposit from copper borate-zlrconyl ammonium complex decomposition) The heat decomposition mechanism for aqueous phenyl mercury salt-zirconyl ammonium carbonate complexes may be explained according to the following complex with phenyl mercury acetate:

The relative insolnbility of the deposit, as compared with phenyl mercury acetate alone, in conjunction with a strong afiinity for cellulose, suggests the following structure for the insoluble residue:

OH O

2.0 grams ofthe borate will complex with 15.6 grams of zirconyl ammonium carbonate from calculation) or to the extent of 2.0% copper borate, by reacting at room temperature over a period of 48 hours. Time offers no difiiculty, since the copper borate is allowed to macerate with occasional agitation over this period, and any quantity may be prepared at one time.

Aqueous padding solutions useful for application to cotton as a fungicide have been found to be preferably stable at room temperatures (about 25 C.) for several weeks. These solutions can be stable indefinitely as long as an upper temperature limit of 50 C. is avoided. Past this upper limit the ingredients become insoluble, which feature becomes an asset in that cotton fabrics treated with the solutions and subsequently cured past the upper limit will acquire and retain fungistatic properties which are stable through launderings and exposure to weather.

The water soluble composition of copper borate-zirconyl ammonium carbonate has been applied from solids concentrations with as low as 0.425% Cu and 2.50% ZrO to cotton cloth (army duck), to produce a good uniform application on the padder, and further cured on the cloth at temperatures about from 100 to 145 C., producing an insoluble blue-green deposit, which contains 0.2% Cu and 1.25% ZrO which deposit withstands a 4-hour water leaching test without loss. The deposit on the cloth possesses inherently qualities of high fungistatic and fungicidal activity, since it contains three known elements of noted fungicidal activity, i.e., copper, zirconium, and boron.

A sample of cloth treated and cured as described above, and having a 0.4% Cu and 2.50% Zr add-on, was buried in a composted soil bed together with an untreated control sample and exposed to microbiological attack for 7 days. Subsequently both samples were removed, and tested for breaking strength. The treated cloth retained 100% of its original strength, while the untreated control had practically disintegrated and retained only 7% of its original strength. Another quality of the cloth treated by the process of this invention is notable water repellency.

Water soluble compositions of phenylmercury salts and zirconyl ammonium carbonate have been applied from solids concentration with as low as 0.5% Hg and 2.50% ZrO where the cloth add-on was 0.25% Hg and 1.25% ZrO Army duck, so treated, received a good, uniform add-on when padded and cured (put in oven while wet) 5 minutes at 145 C. The treatment produced a colorless, insoluble deposit, which withstood a 4-hour water leaching test without loss. The deposit on the cloth possesses high fungistatic and fungicidal activity, since it contains the elements of known fungicidal activity, i.e., mercury and zirconium.

Samples of cloth treated and cured as described above, and having a 0.4% Hg and 2.40% Zr0 add-on, were buried in a composted soil bed together with an untreated control and exposed to microbiological attack for 42 days. Samples of each were periodically removed, and tested for breaking strength. The treated cloth retained 100% of its original strength after 42 days exposure, While the untreated cloth retained only 7% of its original strength at the end of 7 days exposure and was completely disintegrated at the end of the 14th day.

The phenyl mercury acetate and lactate derivatives with zirconyl ammonium carbonate deposited on duck showed 100% retained breaking strength at the end of 28 days of exposure to microbiological attack (burial in the composted bed). Again, it was noted that heat cured deposits of these phenylmercury-zirconyl ammonium carbonate derivatives produce notable water repellency characteristics on cotton cloth.

The following examples are specific cases set forth to illustrate the invention in detail, and percentages are by weight.

Example 1 1.0 gram of copper borate (1 CuO:2B O anhydrous salt and 50 grams of zirconyl ammonium carbonate solution ZrO in water were mixed and allowed to stand for 48 hours at room temperature (25 C.), with occasional agitation. At the end of this time, all of the copper borate had dissolved to produce a dark blue solution of the water soluble composition formed.

Example 2 1.0 gram of copper borate (1 CuO:2B O hydrated (2H O) salt and 50 grams of zirconyl ammonium carbonate solution (10% ZrO in Water were mixed and allowed to stand for 48 hours at room temperature (25 C.), with occasional agitation. At the end of this time all of the copper borate had dissolved to produce a dark blue solution of the water soluble composition formed.

Example 3 2.0 grams of copper borate (1 CuO:2B O hydrated (21-1 0) salt and 50 grams of zirconyl ammonium carbonate solution (10% ZrO in water were mixed and allowed to stand for 48 hours at room temperature (25 C.), with occasional agitation. At the end of this time all of the copper borate had dissolved to produce a dark blue solution with a trace of sediment. This solution, containing 1.70% Cu, was diluted with 150 grams water to produce a 0.42% Cu content. Fifty grams of this solution were diluted with 250 grams of water to produce a 300 gm. solution containing .07% Cu and 0.2% ZrO This solutioin was diluted with an equal weight of water to give a solids of 0.135 A blue color was still noticeable and the solution remained clear.

Example 4 1.0 gram of copper borate (2 CuO:3B O anhydrous salt and 50 grams of zirconyl ammonium carbonate solution (10% ZrO in water were mixed and allowed to stand for 48 hours at room temperature (25 C.), with oc casional agitation. At the end of this time, all of the copper borate had dissolved to produce a dark blue solution. The solution was heated to about 55 C. for one hour. Evidence of dissociation was noted with slight ppt. formation. When heated to C., for 5 minutes, a blue precipitate formed, showing complete dissociation at this temperature, resulting in precipitation of the copper and zirconium ion. The filtered ppt. was not soluble in distilled water.

Example 5 Two grams of copper borate (1 CuO-2B O hydrated (2H O) salt and 50 gins. of zirconyl ammonium carbonate solution (10% ZrO in water were mixed and allowed to stand and macerate for 48 hours at room temperature (25 C.), with occasional agitation. At the end of this time, all of the copper borate had dissolved to produce a dark blue solution with a trace of sediment. This solution, contaiinng 1.70% Cu and 10% ZrO was diluted with 50 gms. of distilled water to produce a dark blue solution containing 0.85% Cu and 5% ZrO This solution was used to pad 8 oz. army duck, using two nips and dips, and passed through tight rolls to give a wet pickup of 50%, equivalent to 0.42% Cu and 2.50% ZrO The wet treated cloth had a pale blue color. Cure was effected at C. for 5 minutes in an electric oven. The cloth developed a pale blue-green color, as a result of the deposition of copper and zirconium ions onto the cloth, as an insoluble compound. Color of the treatment was uniform and not objectionable. Samples of the cured treated cloth were leached for 1 hour with tap water, while others were leached for 4 hours with distilled water. No evidence of loss of treatment through color loss was noted with either leaching procedure and resistance to Wetting was notable. The in situ change from the soluble derivative to the insoluble derivative requires that curing temperature be 145 C. for a 5-minute curing time. Lower temperatures would naturally require a longer time interval.

A section of the cured treated cloth was cut into 5 strips of cloth, 1 inch by 7 inches each, and 5 strips were cut from the untreated cloth, as ontrol. Both samples were buried in the rot bed (composted soil). At the end of a period of 7 days, the samples were dug up and examined. The'control samples were heavily mildewed and showed 7% retained strength. The treated samples showed no evidence of microbiological attack and retained 100% strength.

Example 6 The following three solutions of phenylmercury saltzirconyl ammonium carbonate compositions were prepared for padding onto duck (8 oz.) and subsequent fungicide evaluation (soil burial test):

Solution A 5 gms. zirconyl ammonium carbonate solution (10% ZI'OZ) 1.7 gms. phenyl mercury acetate 50 gms. distilled water Solution A contains 1.0% Hg and 5% ZrO Solution B Solution C- 50 gms. zirconyl ammonium carbonate solution (10% 1.8 gms. phenyl mercury propionate 50 gms. distilled water Solution C contains 1.0% Hg and 5% ZrO These three solutions were prepared by adding the zirconyl ammonium carbonate solution to a weighed quantity of the appropriate phenyl mercury salt at room temperature (25 C.) and warming the mixture to 40? C., While stirring, to effect rapid solubility. The prepared solutions were placed in stoppered containers and retained at room temperature (25 C.) prior to use as padding solutions. Samples of 8 oz. army duck (scoured) were padded twice with the prepared respective solution on a conventional padder, followed by a direct cure at 145 C. for 5 minutes in an electric oven. Add-on (wet pickup of the fabric) was estimated at 49%, giving the treated cloth a content of about 0.49% Hg. and about 2.45% ZrO The treated duck evidenced no loss in breaking strength when compared with an untreated control. At the end of 28 days in a soil (rot) bed, all of the treated samples showed 100% retained breaking strength, while the comparative samples of untreated duck showed only 7% retained breaking strength after one week, and complete disintegration at the end of two weeks soil bed burial. At the end of 6 weeks soil bed burial, the propionate derivative showed 100% retained breaking strength, the acetate derivative showed 77% retained breaking strength, and the lactate derivative showed 34% retained breaking strength.

Example 7 3.6 gms. of phenyl mercury propionate were dissolved in 100 gms. of zirconyl ammonium carbonate solution ZrO- at 40 C., with stirring, to produce a clear solution. Three hundred grams of distilled water were added to produce a clear solution containing 0.5% Hg and 2.50% ZrO A sample of duck was padded with the solution to give a 50% add-on. The treated duck was then cured at 145 C. for 5 minutes to produce a colorless fabric with good band. The theoretical add-ons of 0.25% Hg and 1.25% ZrO were confirmed by X-ray fluorescence analyses.

Example 8 1.0 gram of copper borate (1 CuO'2B O anhydrous and 50 grams of zirconyl ammonium carbonate solution (10% ZrO in Water are mixed and allowed to macerate for 48 hours in a stoppered flask. At the end of this time the copper borate has completely dissolved, and a dark 8 'blue solution results. It contains 0.85% Cu and 10% ZrO or 2% copper borate and 10% ZrO The solution was emptied into an evaporating dish and evaporated to dryness on the hot plate. A dark blue, non-crystalline, water insoluble derivative remains.

Example 9 1.8 grams of phenyl mercury propionate and 50 grams of zirconyl ammonium carbonate solution (10% ZrO in water were mixed at room temperature (25 C.) and stirred. The phenyl mercury salt dissolves to form a water soluble derivative containing 2.06% mercury and 10% ZrO This was evaporated to dryness on the hot plate, resulting in a yellowish-white, non-crystalline, water insoluble derivative.

Example 10 Three samples of duck, which had been padded with a 1CuO-2B O copper borate-zirconyl ammonium carbon ate solution in water to give a theoretical add-on of 0.6% Cu and 5.0% ZIOZ, were analyzed (X-ray) for percent Cu before water washing and after a 30 minute hot (50 C.) tap water wash in one case, and 4 hours distilled water leaching in another case. The percent Cu was found to be 0.6% before wash, and 0.6% Cu after 30 minutes hot tap water wash, and 0.6% Cu after 4 hours distilled water leaching.

I claim:

1. A water soluble composition of copper borate and zirconyl ammonium carbonate having the formula:

2. A process for preparing a water soluble copper borate-zirconyl ammonium carbonate composition comprising mixing 2 to 4 parts by weight of copper borate with about 100 parts by weight of a solution of zirconyl ammonium carbonate containing about 10% by Weight of Z'rO and about by weight of Water, ammonia and carbon dioxide, and heating the resulting mixture at a temperature below 50 C. to dissolve the copper borate and produce the water soluble copper borate-zirconyl ammonium carbonate composition having the formula:

3. A Water insoluble composition of copper borate and zirconyl ammonium carbonate having the formula:

4. A process comprising heating to dryness the Water soluble composition of copper borate and zirconyl ammonium carbonate having the formula:

at a temperature exceeding 50 C. to liberate carbon dioxide, ammonia gas, and water, and produce the water insoluble composition of copper borate and zirconyl am- 5 monium carbonate having the formula:

5. A process comprising heating to dryness the water soluble composition containing copper and zirconium produced by the process of claim 2 at a temperature exceeding C. to liberate carbon dioxide, ammonium gas, and water, and produce a water insoluble composition containing copper and zirconium.

6. A process for preparing a Water soluble composition containing mercury and zirconium comprising about from 1.7 to 1.9 parts by weight of a mercury compound selected from the group consisting of phenyl mercuric acetate, phenyl mercuric lactate, and phenyl mercuric propionate heating the resulting mixture at a temperature below 50 C. to dissolve the mercury compound, and mixing the resulting solution with 50 parts by weight of a solution of zirconyl ammonium carbonate containing from 5 to 10% by Weight of ZrO and from to by weight of water to produce a water soluble composition containing mercury and zirconium.

7. The process of claim 6 wherein the mercury compound is phenyl mercury acetate.

8. The process of claim 6 wherein the mercury compound is phenyl mercury lactate.

9. The process of claim 6 wherein the mercury compound is phenyl mercury propionate.

10. A process comprising heating to dryness the water soluble composition containing mercury and zirconium produced by the process of claim 7 at a temperature exceeding 50 C. to liberate carbon dioxide, ammonia gas, and water, and produce a Water insoluble composition containing mercury and zirconium.

11. A process comprising heating to dryness the water soluble composition containing mercury and zirconium produced by the process of claim 8 at a temperature exceeding 50 C. to liberate carbon dioxide, ammonia gas, and water, and produce a water insoluble composition containing mercury and zirconium.

12. A process comprising heating to dryness the water soluble composition containing mercury and zirconium produced by the process of claim 8 at a temperature exceeding 50 C. to liberate carbon dioxide, ammonia gas, and Water, and produce a water insoluble composition containing mercury and zirconium.

13. A process for rendering cotton fabric rot resistant comprising padding the cotton fabric to a wet pickup of about 50% with an aqueous solution containing the water soluble copper borate-zirconyl ammonium carbonate produced by the process of claim 2 dissolved therein in an amount corresponding to about 5% zirconium and about 0.85% copper to achieve an add-on of at least 2.5% zirconium by Weight and at least 0.42% by weight of copper, and curing the padded fabric at a temperature of about C. for a period of about 5 minutes, the shorter time intervals being employed with the higher temperatures.

14. A process for rendering cotton fabric rot resistant comprising padding the cotton fabric to a wet pickup of about 50% with an aqueous solution containing the water soluble phenyl mercury acetate-zirconyl ammonium carbonate produced by the process of claim 7 dissolved therein in an amount sufficient to achieve an add-on of at least 0.49% by Weight of mercury and about 2.45% by weight of zirconium, and curing the padded fabric at a temperature of about 145 C. for a period of about 5 minutes.

15. A process for rendering cotton fabric rot resistant comprising padding the cotton fabric to a wet pickup of about 50% with an aqueous solution containing the water soluble phenyl mercury lactate-zirconyl ammonium carbonate produced by the process of claim 8 dissolved therein in an amount suflicient to achieve an add-on of at least 0.49% by weight of mercury and about 2.45% by Weight of zirconium, and curing the padded fabric at a temperature of about .145 C. for a period of about 5 minutes.

16. A process for rendering cotton fabric rot resistant comprising padding the cotton fabric to a wet pickup of about 5 0% with an aqueous solution containing the water soluble phenyl mercury propionate-zirconyl ammonium carbonate produced by the process of claim 9 dissolved therein in an amount sufficient to achieve an add-on of at least 0.49% by Weight of mercury and about 2.45% by Weight of zirconium, and curing the padded fabric at a temperature of about 145 C. for a period of about 5 minutes.

References Cited by the Examiner UNITED STATES PATENTS 2,482,816 9/1949 Van Mater 117-121 2,698,263 12/1954 Weick 1l7138.5 3,183,118 5/1965 Conner 117-138.5

MURRAY KATZ, Primary Examiner.

THEODORE G. DAVIS, Assistant Examiner.

Claims

2. A PROCESS FOR PREPARING A WATER SOLUBLE COPPER BORATE-ZIRCONYL AMMONIUM CARBONATE COMPOSITION COMPRISING MIXING 2 TO 4 PARTS BY WEIGHT OF COPPER BORATE WITH ABOUT 100 PARTS BY WEIGHT OF A SOLUTION OF ZIRCONYL AMMONIUM CARBONATE CONTAINING ABOUT 10% BY WEIGHT OF ZRO2 AND ABOUT 90% BY WEIGHT OF WATER, AMMONIA AND CARBON DIOXIDE, AND HEATING THE RESULTING MIXTURE AT A TEMPERATURE BELOW 50*C. TO DISSOLVE THE COPPER BORATE AND PRODUCE THE WATER SOLUBLE COPPER BORATE-ZIRCONYL AMMONIUM CARBONATE COMPOSITION HAVING THE FORMULA:
13. A PROCESS FOR RENDERING COTTON FABRIC ROT RESISTANT COMPRISING PADDING THE COTTON FABRIC TO A WET PICKUP OF ABOUT 50% WITH AN AQUEOUS SOLUTION CONTAINING THE WATER SOLUBLE COPPER BORATE-ZIRCONYL AMMONIUM CARBONATE PORDUCED BY THE PROCESS OF CLAIM 2 DISSOLVED THEREIN IN AN AMOUNT CORRESPONDING TO ABOUT 5% ZIRCONIUM AND ABOUT 0.85% COPPER TO ACHIEVE AN ADD-ON OF AT LEAST 2.5% ZIRCONIUM BY WEIGHT AND AT LEAST 0.42% BY WEIGHT OF COPPER, AND CURING THE PADDED FABRIC AT A TEMPERATURE OF ABOUT 145*C. FOR A PERIOD OF ABOUT 5 MINUTES, THE SHORTER TIME INTERVALS BEING EMPLOYED WITH THE HIGHER TEMPERATURES.